CN110755887B - Preparation method and application of super-infiltrated Janus material - Google Patents
Preparation method and application of super-infiltrated Janus material Download PDFInfo
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- CN110755887B CN110755887B CN201911140590.7A CN201911140590A CN110755887B CN 110755887 B CN110755887 B CN 110755887B CN 201911140590 A CN201911140590 A CN 201911140590A CN 110755887 B CN110755887 B CN 110755887B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
Abstract
The invention relates to the technical field of super-infiltration Janus materials, in particular to a preparation method and application of a super-infiltration Janus material. According to the invention, the mixed solution of ammonium persulfate solution and sodium hydroxide solution is used as a corrosive solution to etch the copper mesh or the copper foam, and a 'loose needle-shaped' nano structure can be distributed on the surface of the copper mesh or the copper foam, so that the copper mesh or the copper foam has super-hydrophilic characteristics; secondly, the super-hydrophilic copper mesh or the super-hydrophilic copper foam obtained by processing the low surface energy gas molecules of the dimethyl siloxane mixed solution through hydrophobization modification and a method of adding water to control the infiltration distance of hydrophobic molecules is used, so that one side of the prepared super-hydrophobic-super-hydrophilic copper foam is super-hydrophilic, the other side of the prepared super-hydrophobic-super-hydrophilic copper foam is super-hydrophobic, and the oil-water separation efficiency is higher (higher than 94%); and the prepared super-hydrophobic-super-hydrophilic copper net enables underwater bubbles to be conducted in a one-way mode in a water environment by means of special wettability of the interface of the super-hydrophobic-super-hydrophilic copper net material.
Description
Technical Field
The invention relates to the technical field of super-infiltration Janus materials, in particular to a preparation method and application of a super-infiltration Janus material.
Background
The wettability of the solid material surface is mainly determined by the synergy of the microstructure and the chemical composition of the solid surface. In recent years, scientific researchers have conducted intensive research on various super-wetting surfaces, and a plurality of preparation methods of super-wetting interface materials are developed. The super-wetting Janus material is an interface material with two surfaces having different wetting characteristics (super-hydrophilic-super-hydrophobic), and has wide application in the fields of ion controllable transportation, oil/water separation, fluid one-way conduction and the like. The super-wetting Janus interface material can be mainly prepared by two methods of asymmetric construction and asymmetric modification. Preparing a hydrophobic polyurethane/hydrophilic vinyl alcohol fiber structure membrane by using an asymmetric construction method and adopting a sequential electrospinning technology to realize the one-way permeation of water droplets (Wu J, Wang N, Wang L, et al. Unidirective water-hybridization composite fibrous electrospinning [ J ]. SoftMatter,2012,8(22): 5996-; by using an asymmetric modification method, a ZnO coating fabric film is modified by super-hydrophobic molecules, and then One side of the fabric is subjected to ultraviolet light degradation treatment to restore the hydrophilicity, so as to obtain the super-hydrophobic and hydrophilic fabric film (Wang H, Zhou H, Yang W, et al. Selective, porous One-Way Oil-Transport Fabrics and the needle Novel for gaining Liquid Surface Tension [ J ]. ACSApplied materials & Interfaces,2015,7(41): 22874-.
However, at present, the steps for preparing the super-infiltrated Janus interface material by using an asymmetric construction and asymmetric modification method are complicated, the operation conditions are not easy to regulate, and the fluid transport direction on a special infiltrated interface is difficult to control, so that the simple construction of the two-dimensional or three-dimensional super-infiltrated Janus interface material and the realization of one-way transport and oil-water separation on a gas-liquid-solid three-phase interface still remain important problems to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method and application of a super-infiltrated Janus material.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a super-infiltrated Janus material, which comprises the following steps:
providing a copper mesh or a copper foam; the aperture of the copper net is 20-100 meshes, and the porosity of the copper foam is 50-90%;
etching the copper mesh or the copper foam in a corrosive liquid to obtain a super-hydrophilic copper mesh or super-hydrophilic copper foam; the corrosive liquid is a mixed liquid of an ammonium persulfate solution and a sodium hydroxide solution;
pre-curing the pre-polymerized dimethyl siloxane solution to obtain pre-cured polydimethylsiloxane;
placing the super-hydrophilic copper mesh or the super-hydrophilic copper foam on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, and simultaneously, dropwise adding deionized water to control the contact time of the super-hydrophilic copper mesh or the super-hydrophilic copper foam and the pre-cured polydimethylsiloxane, adding deionized water to fully soak a hydrophilic layer, and curing to obtain the super-soaked Janus material;
the super-wetting Janus material is a super-hydrophobic-super-hydrophilic copper mesh or super-hydrophobic-super-hydrophilic copper foam.
Preferably, before the etching, the method further comprises pretreating the copper mesh or the copper foam;
the pretreatment process comprises the following steps: and under the ultrasonic condition, sequentially cleaning the copper mesh or the copper foam by adopting absolute ethyl alcohol and hydrochloric acid.
Preferably, the concentration of the ammonium persulfate solution is 0.012-0.017 mol/L; the concentration of the sodium hydroxide solution is 4.5-5.5 mol/L;
the volume ratio of the ammonium persulfate solution to the sodium hydroxide solution is (0.8-1.2): 1.
preferably, the etching temperature is 25-30 ℃, and the etching time is 8 min.
Preferably, the preparation method of the prepolymerized dimethylsiloxane solution includes the steps of:
and mixing dimethyl siloxane and a cross-linking agent to obtain the pre-polymerized dimethyl siloxane solution.
Preferably, the mass ratio of the dimethyl siloxane to the cross-linking agent is 10: 1.
Preferably, the pre-curing temperature is 60 ℃, and the pre-curing time is 25-30 min.
Preferably, the contact time of the super-hydrophilic copper mesh and the pre-cured polydimethylsiloxane is 1-6 s;
the curing temperature is 60 ℃, and the curing time is 4-6 h.
Preferably, the contact time of the super-hydrophilic copper foam and the pre-cured polydimethylsiloxane is 1-60 s;
the curing temperature is 60 ℃, and the curing time is 4-6 h.
The invention also provides application of the super-infiltrated Janus material prepared by the preparation method in the technical scheme in the fields of oil/water separation and fluid one-way conduction.
The invention provides a preparation method of a super-infiltrated Janus material, which comprises the following steps: providing a copper mesh or a copper foam; the aperture of the copper net is 20-100 meshes, and the porosity of the copper foam is 50-90%; etching the copper mesh or the copper foam in a corrosive liquid to obtain a super-hydrophilic copper mesh or super-hydrophilic copper foam; the corrosive liquid is a mixed liquid of an ammonium persulfate solution and a sodium hydroxide solution; pre-curing the pre-polymerized dimethyl siloxane solution to obtain pre-cured polydimethylsiloxane; placing the super-hydrophilic copper mesh or the super-hydrophilic copper foam on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, and simultaneously dropwise adding deionized water to control the contact time of the super-hydrophilic copper mesh or the super-hydrophilic copper foam and the pre-cured polydimethylsiloxane, and then curing to obtain the super-infiltrated Janus material; the super-wetting Janus material is a super-hydrophobic-super-hydrophilic copper mesh or super-hydrophobic-super-hydrophilic copper foam. According to the invention, the mixed solution of ammonium persulfate solution and sodium hydroxide solution is used as a corrosive solution to etch the copper mesh or the copper foam, and a 'loose needle-shaped' nano structure can be distributed on the surface of the copper mesh or the copper foam, so that the copper mesh or the copper foam has super-hydrophilic characteristics; secondly, the super-hydrophilic copper mesh or the super-hydrophilic copper foam obtained by processing the low surface energy gas molecules of dimethyl siloxane through hydrophobic modification and a method of adding water to control the infiltration distance of hydrophobic molecules is utilized, so that one side of the prepared super-hydrophobic-super-hydrophilic copper foam is super-hydrophilic, the other side of the prepared super-hydrophobic-super-hydrophilic copper foam is super-hydrophobic, and the super-hydrophilic-super-hydrophilic copper foam has higher oil-water separation efficiency (94%); the prepared super-hydrophobic-super-hydrophilic copper mesh enables underwater bubbles to be conducted in a single direction in a water environment by means of special wettability of a super-hydrophobic-super-hydrophilic copper mesh material interface, and has great application in the fields of microfluidic devices and intelligent materials;
meanwhile, the preparation method provided by the invention has a wide application range, and can be suitable for other metal mesh materials, three-dimensional metal foam materials and metal plates; the method is simple and convenient, consumes less time, has cheap and easily obtained raw materials, has no pollution on the used materials, and can be recycled.
Drawings
FIG. 1 is a flow chart of a method for preparing a super-infiltrated Janus material according to the present invention;
FIG. 2 is a photograph showing the static water contact angle of the superhydrophobic-superhydrophilic copper mesh prepared in example 4 of the present invention (a is the superhydrophobic side on top, and b is the hydrophilic side on top);
FIG. 3 is an SEM image of the super-hydrophobic-super-hydrophilic copper mesh prepared in example 4 of the present invention (a is the super-hydrophobic side, b is the hydrophilic side);
fig. 4 is a diagram of an actual process of unidirectional underwater bubble conduction of the superhydrophobic-superhydrophilic copper mesh prepared in embodiment 4 of the present invention (a is a diagram of a process of transporting bubbles from a lower superhydrophobic side to a lower hydrophilic side to an upper hydrophilic side, and b is a diagram of a process of transporting bubbles from a lower superhydrophobic side to a lower hydrophilic side to an upper hydrophilic side);
fig. 5 is a schematic diagram of the principle that the superhydrophobic-superhydrophilic copper mesh prepared in embodiment 4 of the present invention is used for unidirectional conduction of underwater bubbles (a is that the superhydrophobic side is on the lower/hydrophilic side, and b is that the hydrophilic side is on the lower/superhydrophobic side);
FIG. 6 is an optical picture of superhydrophobic-superhydrophilic copper foam prepared in example 7 of the present invention;
fig. 7 is an underwater superhydrophobic side optical picture (a), a static water contact angle picture (a '), an underwater superhydrophilic side optical picture (b) and a static water contact angle picture (b') of the superhydrophobic-superhydrophilic copper foam prepared in example 7 of the present invention;
FIG. 8 is a schematic view of an apparatus for oil-water separation using superhydrophobic-superhydrophilic copper foam of the present invention;
FIG. 9 is an optical photograph (a) of a light oil (density less than water)/water mixed solution separation actual process and an optical photograph (b) of a heavy oil (density greater than water)/water mixed solution separation actual process according to the present invention.
Detailed Description
The invention provides a preparation method of a super-infiltrated Janus material, which comprises the following steps:
providing a copper mesh or a copper foam; the aperture of the copper net is 20-100 meshes, and the porosity of the copper foam is 50-90%;
etching the copper mesh or the copper foam in a corrosive liquid to obtain a super-hydrophilic copper mesh or super-hydrophilic copper foam; the corrosive liquid is a mixed liquid of an ammonium persulfate solution and a sodium hydroxide solution;
pre-curing the pre-polymerized dimethyl siloxane solution to obtain pre-cured polydimethylsiloxane;
placing the super-hydrophilic copper mesh or the super-hydrophilic copper foam on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, and simultaneously, after controlling the contact time of the super-hydrophilic copper mesh or the super-hydrophilic copper foam and the pre-cured polydimethylsiloxane by dropping deionized water, adding deionized water to fully soak a hydrophilic layer for curing to obtain the super-soaked Janus material (shown in figure 1);
the super-wetting Janus material is a super-hydrophobic-super-hydrophilic copper mesh or super-hydrophobic-super-hydrophilic copper foam.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
Providing a copper mesh or a copper foam; the aperture of the copper net is 20-100 meshes, and the porosity of the copper foam is 50-90%. In the present invention, the pore size of the copper mesh is preferably 20 mesh, 30 mesh, 60 mesh, 80 mesh or 100 mesh. In the present invention, the thickness of the copper foam is preferably 2 mm.
The preparation method provided by the invention also comprises the steps of etching the copper mesh or the copper foam in corrosive liquid to obtain a super-hydrophilic copper mesh or super-hydrophilic copper foam; the corrosive liquid is a mixed liquid of an ammonium persulfate solution and a sodium hydroxide solution.
In the invention, before the etching, the method also preferably comprises the step of pretreating the copper mesh or the copper foam; the pretreatment process is preferably as follows: and under the ultrasonic condition, sequentially cleaning the copper mesh or the copper foam by adopting absolute ethyl alcohol and hydrochloric acid. The present invention does not have any particular limitation on the frequency of the ultrasound, and may be performed using an ultrasound frequency known to those skilled in the art. In the invention, when the absolute ethyl alcohol is adopted for cleaning, the ultrasonic time is preferably 20min, and the cleaning frequency is preferably 3 times; after the cleaning with the absolute ethyl alcohol is completed, the invention also preferably comprises washing with a large amount of deionized water, and the invention has no special limitation on the above process. In the invention, when the hydrochloric acid is used for cleaning, the concentration of the hydrochloric acid is preferably 1mol/L, and the time of ultrasonic treatment is preferably 10 min; after the hydrochloric acid is adopted for cleaning, the method also preferably comprises the steps of washing with a large amount of deionized water and drying. The present invention is not limited to any particular process for washing and drying, and may be carried out by a process known to those skilled in the art.
In the invention, the concentration of the ammonium persulfate solution is preferably 0.012-0.017 mol/L, more preferably 0.013-0.016 mol/L, and most preferably 0.014-0.015 mol/L; the concentration of the sodium hydroxide solution is preferably 4.5-5.5 mol/L, and more preferably 4.8-5.2 mol/L. In the invention, the volume ratio of the ammonium persulfate solution to the sodium hydroxide solution is preferably (0.8-1.2): 1, more preferably (0.9 to 1.1): 1.
in the invention, the etching temperature is preferably 25-30 ℃; the etching time is preferably 8 min.
After the etching is finished, the invention also preferably comprises the steps of cleaning by adopting a large amount of deionized water and drying at room temperature; the washing and drying process of the present invention is not particularly limited, and may be performed by a process known to those skilled in the art.
The preparation method also comprises the step of pre-curing the pre-polymerized dimethyl siloxane solution to obtain pre-cured polydimethylsiloxane.
In the present invention, the method for preparing the prepolymerized dimethylsiloxane solution preferably comprises the steps of: and mixing dimethyl siloxane and a cross-linking agent to obtain the pre-polymerized dimethyl siloxane solution. In the invention, the dimethyl siloxane and the cross-linking agent are preferably commercially available products, and more preferably Dow Corning 184 silicone rubber SYLGARD pouring sealant PDMS polydimethylsiloxane (wherein the dimethyl siloxane and the cross-linking agent are used together); the mass ratio of the dimethylsiloxane monomer solution to the crosslinking agent is preferably 10: 1. In the present invention, the mixing is preferably carried out under stirring conditions, and the stirring is not particularly limited in the present invention and may be carried out under conditions well known to those skilled in the art.
In the present invention, before the pre-curing, the pre-polymerized dimethylsiloxane solution is preferably subjected to vacuum filtration; the time of the vacuum filtration is preferably 30 min; other conditions for the vacuum filtration are not particularly limited in the present invention, and those well known to those skilled in the art may be used.
In the invention, the pre-curing temperature is preferably 60 ℃, and the pre-curing time is preferably 25-30 min, and more preferably 26-28 min. In the present invention, the pre-curing is preferably carried out in an oven.
After the pre-cured polydimethylsiloxane is obtained, the super-hydrophilic copper mesh or the super-hydrophilic copper foam is placed on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, and meanwhile, deionized water is dripped to control the contact time of the super-hydrophilic copper mesh or the super-hydrophilic copper foam and the pre-cured polydimethylsiloxane, and then the deionized water is added to fully soak the hydrophilic layer for curing, so that the super-infiltrated Janus material is obtained.
In the present invention, the temperature during the dropping of deionized water is preferably 60 ℃.
In the invention, the contact time of the super-hydrophilic copper mesh and the pre-cured polydimethylsiloxane is preferably 1-6 s, and more preferably 3 s; the temperature of the curing is preferably 60 ℃; the curing time is preferably 4-6 hours, and more preferably 4.5-5.5 hours. In the invention, the depth of the siloxane hydrophobic molecules entering the material can be regulated by regulating the contact time.
In the invention, the contact time of the super-hydrophilic copper foam and the pre-cured polydimethylsiloxane is preferably 1-60 s, and more preferably 30 s; the curing temperature is 60 ℃, and the curing time is preferably 4-6 hours, more preferably 4.5-5.5 hours. In the invention, the depth of the siloxane hydrophobic molecules entering the material can be regulated by regulating the contact time.
The invention also provides application of the super-infiltrated Janus material prepared by the preparation method in the technical scheme in the fields of oil/water separation and fluid one-way conduction. The method of the present invention is not particularly limited, and the method may be applied by a method known to those skilled in the art.
The following will explain the preparation method and application of the super-infiltrated Janus material provided by the present invention in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Providing a copper net (the aperture is 20 meshes); ultrasonically cleaning the copper mesh in absolute ethyl alcohol for 20min for 3 times, cleaning the copper mesh by using a large amount of deionized water, then placing the copper mesh in a 1mol/L hydrochloric acid solution for ultrasonically cleaning for 10min, cleaning the copper material by using a large amount of deionized water, and drying the copper mesh at room temperature for later use;
mixing an ammonium persulfate solution with the concentration of 0.015mol/L and a sodium hydroxide solution with the concentration of 5mol/L according to the volume ratio of 1:1 to obtain a corrosive liquid;
placing the pretreated copper mesh in the corrosive liquid for etching (the temperature is 30 ℃ and the time is 8min), cleaning with a large amount of deionized water, and drying at room temperature to obtain a super-hydrophilic copper mesh;
mixing dimethyl siloxane and a cross-linking agent (the mass ratio is 10:1), uniformly stirring, and carrying out vacuum filtration for 30min to remove bubbles in the obtained dimethyl siloxane solution; placing in an oven for pre-curing (60 deg.C, 28min) to obtain pre-cured polydimethylsiloxane;
and (2) placing the super-hydrophilic copper mesh on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, simultaneously dropwise adding deionized water to control the contact time (3s) of the super-hydrophilic copper mesh and the pre-cured polydimethylsiloxane, further regulating the depth (0.3mm) of siloxane hydrophobic molecules entering the material, adding sufficient deionized water to fully soak the hydrophilic layer, and curing (60 ℃, 5h) to obtain the super-infiltrated Janus material.
Example 2
Providing a copper net (with the aperture of 30 meshes); ultrasonically cleaning the copper mesh in absolute ethyl alcohol for 20min for 3 times, cleaning the copper mesh by using a large amount of deionized water, then placing the copper mesh in a 1mol/L hydrochloric acid solution for ultrasonically cleaning for 10min, cleaning the copper material by using a large amount of deionized water, and drying the copper mesh at room temperature for later use;
mixing an ammonium persulfate solution with the concentration of 0.015mol/L and a sodium hydroxide solution with the concentration of 5mol/L according to the volume ratio of 1:1 to obtain a corrosive liquid;
placing the pretreated copper mesh in the corrosive liquid for etching (the temperature is 30 ℃ and the time is 8min), cleaning with a large amount of deionized water, and drying at room temperature to obtain a super-hydrophilic copper mesh;
mixing dimethyl siloxane and a cross-linking agent (the mass ratio is 10:1), uniformly stirring, and carrying out vacuum filtration for 30min to remove bubbles in the obtained dimethyl siloxane solution; placing in an oven for pre-curing (60 deg.C, 28min) to obtain pre-cured polydimethylsiloxane;
and (2) placing the super-hydrophilic copper mesh on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, simultaneously dropwise adding deionized water to control the contact time (3s) of the super-hydrophilic copper mesh and the pre-cured polydimethylsiloxane, further regulating the depth (0.2mm) of siloxane hydrophobic molecules entering the material, adding sufficient deionized water to fully soak the hydrophilic layer, and heating for curing (60 ℃, 5h) to obtain the super-soaked Janus material.
Example 3
Providing a copper net (with the aperture of 60 meshes); ultrasonically cleaning the copper mesh in absolute ethyl alcohol for 20min for 3 times, cleaning the copper mesh by using a large amount of deionized water, then placing the copper mesh in a 1mol/L hydrochloric acid solution for ultrasonically cleaning for 10min, cleaning the copper material by using a large amount of deionized water, and drying the copper mesh at room temperature for later use;
mixing an ammonium persulfate solution with the concentration of 0.015mol/L and a sodium hydroxide solution with the concentration of 5mol/L according to the volume ratio of 1:1 to obtain a corrosive liquid;
placing the pretreated copper mesh in the corrosive liquid for etching (the temperature is 30 ℃ and the time is 8min), cleaning with a large amount of deionized water, and drying at room temperature to obtain a super-hydrophilic copper mesh;
mixing dimethyl siloxane and a cross-linking agent (the mass ratio is 10:1), uniformly stirring, and carrying out vacuum filtration for 30min to remove bubbles in the obtained dimethyl siloxane solution; placing in an oven for pre-curing (60 deg.C, 28min) to obtain pre-cured polydimethylsiloxane;
and (2) placing the super-hydrophilic copper mesh on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, simultaneously dropwise adding deionized water to control the contact time (3s) of the super-hydrophilic copper mesh and the pre-cured polydimethylsiloxane, further regulating the depth (0.1mm) of siloxane hydrophobic molecules entering the material, adding sufficient deionized water to fully soak the hydrophilic layer, and heating for curing (60 ℃, 5h) to obtain the super-soaked Janus material.
Example 4
Providing a copper net (the aperture is 80 meshes); ultrasonically cleaning the copper mesh in absolute ethyl alcohol for 20min for 3 times, cleaning the copper mesh by using a large amount of deionized water, then placing the copper mesh in a 1mol/L hydrochloric acid solution for ultrasonically cleaning for 10min, cleaning the copper material by using a large amount of deionized water, and drying the copper mesh at room temperature for later use;
mixing an ammonium persulfate solution with the concentration of 0.015mol/L and a sodium hydroxide solution with the concentration of 5mol/L according to the volume ratio of 1:1 to obtain a corrosive liquid;
placing the pretreated copper mesh in the corrosive liquid for etching (the temperature is 30 ℃ and the time is 8min), cleaning with a large amount of deionized water, and drying at room temperature to obtain a super-hydrophilic copper mesh;
mixing dimethyl siloxane and a cross-linking agent (the mass ratio is 10:1), uniformly stirring, and carrying out vacuum filtration for 30min to remove bubbles in the obtained dimethyl siloxane solution; placing in an oven for pre-curing (60 deg.C, 28min) to obtain pre-cured polydimethylsiloxane;
placing the super-hydrophilic copper net on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, simultaneously dropwise adding deionized water to control the contact time (3s) of the super-hydrophilic copper net and the pre-cured polydimethylsiloxane, further regulating the depth (0.07) of siloxane hydrophobic molecules entering a material, adding sufficient deionized water to fully impregnate a hydrophilic layer, and heating for curing (60 ℃, 5 hours) to obtain the super-impregnated Janus material;
FIG. 2 is a static water contact angle picture of the super-hydrophobic-super-hydrophilic copper mesh prepared in example 4 of the present invention (a is a super-hydrophobic side on top, and b is a hydrophilic side on top), and it can be seen from FIG. 2 that the present invention successfully constructs the super-hydrophobic-super-hydrophilic copper mesh;
fig. 3 is an SEM image of the superhydrophobic-superhydrophilic copper mesh prepared in example 4 of the present invention (a is a superhydrophobic side, and b is a hydrophilic side), and it can be seen from fig. 3 that the two-sided structure and chemical composition of the superhydrophobic Janus material have superhydrophobic and hydrophilic properties;
fig. 4 is a diagram of an actual process of unidirectional underwater bubble conduction of the super-hydrophobic-super-hydrophilic copper mesh prepared in embodiment 4 of the present invention (a is a diagram of a process of transporting bubbles from a lower-hydrophilic side to an upper side at an underwater super-hydrophobic side, and b is a diagram of a process of transporting bubbles from a lower-hydrophilic side to an upper side at an underwater super-hydrophobic side at a super-hydrophobic side), and as can be seen from fig. 4, the super-infiltrated Janus material can realize unidirectional underwater bubble conduction;
fig. 5 is a schematic diagram of the principle that the superhydrophobic-superhydrophilic copper mesh prepared in embodiment 4 of the present invention is used for unidirectional conduction of underwater bubbles (a is that the superhydrophobic side is on the lower/hydrophilic side, and b is that the hydrophilic side is on the lower/superhydrophobic side); as can be seen from fig. 5, when the super-infiltrated Janus material is used for an underwater bubble unidirectional conduction mechanism, when the super-hydrophobic side of the super-infiltrated Janus material is on the lower hydrophilic side, the bubbles spread on the lower super-hydrophobic side and cannot penetrate through the copper mesh; when the super-hydrophobic side of the super-infiltrated Janus material is positioned below the upper hydrophilic side, the air bubbles are firstly adsorbed on the hydrophilic side, and under the action of Laplace pressure, the air bubbles penetrate through the copper mesh in a mode that the small air bubbles are fused with the air film on the surface of the upper super-hydrophobic layer.
Example 5
Providing a copper net (the aperture is 100 meshes); ultrasonically cleaning the copper mesh in absolute ethyl alcohol for 20min for 3 times, cleaning the copper mesh by using a large amount of deionized water, then placing the copper mesh in a 1mol/L hydrochloric acid solution for ultrasonically cleaning for 10min, cleaning the copper material by using a large amount of deionized water, and drying the copper mesh at room temperature for later use;
mixing an ammonium persulfate solution with the concentration of 0.015mol/L and a sodium hydroxide solution with the concentration of 5mol/L according to the volume ratio of 1:1 to obtain a corrosive liquid;
placing the pretreated copper mesh in the corrosive liquid for etching (the temperature is 30 ℃ and the time is 8min), cleaning with a large amount of deionized water, and drying at room temperature to obtain a super-hydrophilic copper mesh;
mixing dimethyl siloxane and a cross-linking agent (the mass ratio is 10:1), uniformly stirring, and carrying out vacuum filtration for 30min to remove bubbles in the obtained dimethyl siloxane solution; placing in an oven for pre-curing (60 deg.C, 28min) to obtain pre-cured polydimethylsiloxane;
and (2) placing the super-hydrophilic copper mesh on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, simultaneously dropwise adding deionized water to control the contact time (3s) of the super-hydrophilic copper mesh and the pre-cured polydimethylsiloxane, further regulating the depth (0.05mm) of siloxane hydrophobic molecules entering the material, adding sufficient deionized water to fully soak the hydrophilic layer, and heating for curing (60 ℃, 5h) to obtain the super-soaked Janus material.
Example 6
Providing copper foam (the thickness is 2mm, and the porosity is 50-90%); ultrasonically cleaning the copper foam in absolute ethyl alcohol for 20min for 3 times, cleaning the copper foam by using a large amount of deionized water, then placing the copper foam in a 1mol/L hydrochloric acid solution for ultrasonically cleaning for 10min, cleaning the copper material by using a large amount of deionized water, and drying the copper foam at room temperature for later use;
mixing an ammonium persulfate solution with the concentration of 0.015mol/L and a sodium hydroxide solution with the concentration of 5mol/L according to the volume ratio of 1:1 to obtain a corrosive liquid;
placing the pretreated copper mesh in the corrosive liquid for etching (the temperature is 30 ℃ and the time is 8min), cleaning with a large amount of deionized water, and drying at room temperature to obtain a super-hydrophilic copper mesh;
mixing dimethyl siloxane and a cross-linking agent (the mass ratio is 10:1), uniformly stirring, and carrying out vacuum filtration for 30min to remove bubbles in the obtained dimethyl siloxane solution; placing in an oven for pre-curing (60 deg.C, 28min) to obtain pre-cured polydimethylsiloxane;
and (2) placing the super-hydrophilic copper mesh on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, simultaneously dropwise adding deionized water to control the contact time (30s) of the super-hydrophilic copper mesh and the pre-cured polydimethylsiloxane, further regulating the depth (0.5mm) of siloxane hydrophobic molecules entering the material, adding sufficient deionized water to fully soak the hydrophilic layer, and heating for curing (60 ℃, 5h) to obtain the super-soaked Janus material.
Example 7
Providing copper foam (the thickness is 2mm, and the porosity is 50-90%); ultrasonically cleaning the foam in absolute ethyl alcohol for 20min for 3 times, cleaning the foam by using a large amount of deionized water, then placing the foam in a 1mol/L hydrochloric acid solution for ultrasonically cleaning for 10min, cleaning the copper material by using a large amount of deionized water, and drying the copper material at room temperature for later use;
according to the volume ratio of 1:1, mixing an ammonium persulfate solution with the concentration of 0.015mol/L and a sodium hydroxide solution with the concentration of 5mol/L to obtain a corrosive solution;
placing the pretreated foam in the corrosive liquid for etching (the temperature is 30 ℃ and the time is 8min), cleaning with a large amount of deionized water, and drying at room temperature to obtain super-hydrophilic foam;
mixing dimethyl siloxane and a cross-linking agent (the mass ratio is 10:1), uniformly stirring, and carrying out vacuum filtration for 30min to remove bubbles in the obtained dimethyl siloxane solution; placing in an oven for pre-curing (60 deg.C, 28min) to obtain pre-cured polydimethylsiloxane;
placing the super-hydrophilic foam on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, simultaneously dropwise adding deionized water to control the contact time (60s) of the super-hydrophilic copper mesh and the pre-cured polydimethylsiloxane, further regulating the depth (1.0mm) of siloxane hydrophobic molecules entering a material, adding sufficient deionized water to fully impregnate a hydrophilic layer, and heating for curing (60 ℃, 5h) to obtain the super-impregnated Janus material;
FIG. 6 is an optical picture of superhydrophobic-superhydrophilic copper foam prepared in example 7 of the present invention; as can be seen from FIG. 6, the super-infiltrated Janus material has been successfully constructed;
fig. 7 is an underwater superhydrophobic side optical picture (a), a static water contact angle picture (a '), an underwater superhydrophilic side optical picture (b) and a static water contact angle picture (b') of the superhydrophobic-superhydrophilic copper foam prepared in example 7 of the present invention; as can be seen from FIG. 7, the super-infiltrated Janus material has an underwater silver mirror effect, and the super-hydrophilic side is super-hydrophilic under water.
Test example
Immersing the super-infiltrated Janus material prepared in the embodiment 1-5 under water, introducing small air bubbles through a micro-injection pump at the speed of 0.5mL/min under water, and testing the conductivity of the air bubbles, wherein the result shows that when the super-hydrophobic side of the copper mesh is on top and the hydrophilic side is on bottom, the small air bubbles can pass through the copper mesh under the action of Laplace pressure; when the super-hydrophobic side of the copper mesh is arranged below, and the hydrophilic side is arranged above, the copper mesh cannot penetrate through the copper mesh, and the copper mesh is only horizontally spread on the super-hydrophobic layer, so that the one-way conduction of underwater bubbles on the super-hydrophobic-super-hydrophilic copper mesh is realized.
The practical process of the underwater bubble unidirectional conduction of the super-infiltrated Janus material obtained in the example 4 is shown in FIG. 4, and as can be seen from FIG. 4, when the super-hydrophobic side of the copper mesh is arranged upwards and the hydrophilic side is arranged downwards, small bubbles can pass through the copper mesh under the action of Laplace pressure; on the contrary, when the super-hydrophobic side of the copper mesh is on the lower-hydrophilic side, the copper mesh cannot penetrate through the copper mesh, and only horizontally spreads on the super-hydrophobic side;
the super-infiltrated Janus material prepared in example 7 was used for separation of a mixed solution of light oil (an organic solvent with density less than water, 0.78g/mL of cyclohexane, 0.866g/mL of toluene, 0.86g/mL of xylene or 0.66g/mL of petroleum ether) and water. As shown in figure 8, the oil-water separation device is characterized in that glass tubes with the diameter of 16mm are connected through tetrafluoroethylene sleeves, the super-infiltrated Janus material is cut to a proper size and placed in the middle of the tetrafluoroethylene sleeves. When the separation light oil is mixed with water, the super-infiltration Janus material is arranged with the hydrophilic side on the upper side and the super-hydrophobic side on the lower side, water penetrates through the super-infiltration Janus material under the action of gravity, the light oil is retained on the super-infiltration Janus material, and efficient separation of the light oil and the water is achieved. The separation efficiency of the separation process is higher than 94%;
the super-infiltrated Janus material prepared in example 7 was used for separation of a mixed solution of heavy oil (an organic solvent having a density greater than that of water, the heavy oil being 1.235g/mL of 1, 2-dichloroethane, 1.484g/mL of chloroform, 1.595g/mL of carbon tetrachloride or 1.1058g/mL of chlorobenzene) and water. The oil-water separation device is shown in fig. 8, a glass tube with the diameter of 16mm is connected through a tetrafluoroethylene sleeve, the super-infiltrated Janus material is cut to a proper size, and the super-infiltrated Janus material is placed in the middle of the tetrafluoroethylene sleeve. When the heavy oil and the water are separated and mixed, the super-hydrophilic side of the super-infiltrated Janus material is arranged at the lower part, the super-hydrophobic side is arranged at the upper part, the heavy oil penetrates through the super-infiltrated Janus material under the action of gravity, and the water is retained on the super-infiltrated Janus material, so that the high-efficiency separation of the heavy oil and the water is realized. The separation efficiency of the separation process is higher than 94%.
Fig. 9 shows an optical photograph of the above-mentioned separation process of water light oil/water and heavy oil/water, and it can be seen from fig. 9 that the prepared superhydrophobic-superhydrophilic copper foam can realize effective separation of oil-water mixtures with different densities under water, and can realize separation of heavy oil and water mixed solution when the superhydrophobic side is on the upper superhydrophilic side and the superhydrophilic side is on the lower side; when the super-hydrophobic side is on the lower super-hydrophilic side and on the upper super-hydrophilic side, the separation of light oil and water mixed solution can be realized.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of super-infiltrated Janus material is characterized by comprising the following steps:
providing a copper mesh or a copper foam; the aperture of the copper net is 20-100 meshes, the porosity of the copper foam is 50-90%, and the thickness of the copper foam is 2 mm;
etching the copper mesh or the copper foam in a corrosive liquid to obtain a super-hydrophilic copper mesh or super-hydrophilic copper foam; the corrosive liquid is a mixed liquid of an ammonium persulfate solution and a sodium hydroxide solution;
carrying out vacuum filtration on the pre-polymerized dimethyl siloxane solution for 30min, and then carrying out pre-curing to obtain pre-cured polydimethylsiloxane;
placing the super-hydrophilic copper mesh or the super-hydrophilic copper foam on the surface of the pre-cured polydimethylsiloxane for hydrophobic modification, and simultaneously, dropwise adding deionized water to control the contact time of the super-hydrophilic copper mesh or the super-hydrophilic copper foam and the pre-cured polydimethylsiloxane, adding deionized water to fully soak a hydrophilic layer, and curing to obtain the super-soaked Janus material;
the super-wetting Janus material is a super-hydrophobic-super-hydrophilic copper mesh or super-hydrophobic-super-hydrophilic copper foam;
the concentration of the ammonium persulfate solution is 0.012-0.017 mol/L; the concentration of the sodium hydroxide solution is 4.5-5.5 mol/L;
the volume ratio of the ammonium persulfate solution to the sodium hydroxide solution is (0.8-1.2): 1;
the contact time of the super-hydrophilic copper mesh and the pre-cured polydimethylsiloxane is 1-6 s;
the contact time of the super-hydrophilic copper foam and the pre-cured polydimethylsiloxane is 1-60 s;
the preparation method of the pre-polymerized dimethyl siloxane solution comprises the following steps:
and mixing dimethyl siloxane and a cross-linking agent to obtain the pre-polymerized dimethyl siloxane solution.
2. The method according to claim 1, further comprising, before the etching, pretreating the copper mesh or the copper foam;
the pretreatment process comprises the following steps: and under the ultrasonic condition, sequentially cleaning the copper mesh or the copper foam by adopting absolute ethyl alcohol and hydrochloric acid.
3. The preparation method according to claim 1, wherein the etching temperature is 25-30 ℃ and the etching time is 8 min.
4. The method according to claim 1, wherein the mass ratio of the dimethylsiloxane to the crosslinking agent is 10: 1.
5. The method according to claim 1, wherein the pre-curing temperature is 60 ℃ and the pre-curing time is 25 to 30 min.
6. The preparation method according to claim 1, wherein the curing temperature is 60 ℃ and the curing time is 4-6 h.
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| CN111604032B (en) * | 2020-06-02 | 2021-04-02 | 山东建筑大学 | Janus nitrogen-doped carbon nanofiber film and preparation method and application thereof |
| CN111871001B (en) * | 2020-07-07 | 2022-01-14 | 中山大学 | Janus type material with one-way water transmission property and preparation method and application thereof |
| CN112774256B (en) * | 2020-12-17 | 2022-02-18 | 北京航空航天大学 | Preparation method and application of Janus copper mesh with heterostructure in air |
| CN113082853B (en) * | 2021-03-31 | 2022-05-24 | 华南理工大学 | Three-dimensional Janus stainless steel mesh capable of separating emulsified oil and water and preparation method thereof |
| CN113665194B (en) * | 2021-08-30 | 2023-01-03 | 电子科技大学 | Waterproof breathable composite net and preparation method and application thereof |
| CN113786739B (en) * | 2021-09-02 | 2023-04-28 | 湖北大学 | Preparation method of Janus membrane with micro-nanowire channel structure |
| CN115006996B (en) * | 2022-06-15 | 2023-05-05 | 南京林业大学 | Janus wood film with asymmetric wettability, preparation method and application thereof |
| CN115138221B (en) * | 2022-07-26 | 2023-07-18 | 南京工业大学 | Application and preparation method of Janus ceramic membrane in dispersion strengthening gas distribution process |
| CN115491020B (en) * | 2022-09-21 | 2023-05-16 | 青岛科技大学 | Janus type composite foam photo-thermal functional material and preparation method and application thereof |
| CN116672900B (en) * | 2023-01-11 | 2023-11-17 | 赣南师范大学 | Preparation method and application of super-hydrophobic copper mesh/covalent organic polymer composite film |
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| CN106433437B (en) * | 2016-09-14 | 2019-01-25 | 陕西科技大学 | The method of spray coating method preparation super-hydrophobic super-oleophylic copper mesh |
| CN110038569B (en) * | 2019-05-22 | 2021-11-19 | 安徽理工大学 | Janus Cu (OH)2@Cu2O/Cu net and preparation method and application thereof |
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